CN103003259A - Processes for the production of hydrogenated products and derivatives thereof - Google Patents

Processes for the production of hydrogenated products and derivatives thereof Download PDF

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Publication number
CN103003259A
CN103003259A CN2011800292396A CN201180029239A CN103003259A CN 103003259 A CN103003259 A CN 103003259A CN 2011800292396 A CN2011800292396 A CN 2011800292396A CN 201180029239 A CN201180029239 A CN 201180029239A CN 103003259 A CN103003259 A CN 103003259A
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fermented liquid
liquid
water
solid
ammonia
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奥兰·S·弗吕谢
利奥·E·曼策
迪卢姆·杜努维拉
布莱恩·T·科恩
布鲁克·A·阿尔宾
奈·A·克林顿
伯纳德·D·东贝克
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Bioamber SAS
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Bioamber SAS
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D313/00Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
    • C07D313/02Seven-membered rings
    • C07D313/04Seven-membered rings not condensed with other rings
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/02Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D223/00Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom
    • C07D223/02Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D223/06Heterocyclic compounds containing seven-membered rings having one nitrogen atom as the only ring hetero atom not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D223/08Oxygen atoms
    • C07D223/10Oxygen atoms attached in position 2
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P17/00Preparation of heterocyclic carbon compounds with only O, N, S, Se or Te as ring hetero atoms
    • C12P17/02Oxygen as only ring hetero atoms
    • C12P17/08Oxygen as only ring hetero atoms containing a hetero ring of at least seven ring members, e.g. zearalenone, macrolide aglycons
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00Preparation of oxygen-containing organic compounds
    • C12P7/40Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • C12P7/44Polycarboxylic acids

Abstract

A process for making a hydrogenated product comprising caprolactone (CLO) and 1,6-hexanediol (HDO) and derivatives thereof from adipic acid (AA) obtained from fermentation broths containing diammonium adipate (DAA) or monoammonium adipate (MAA).

Description

The preparation method of hydrogenated products and derivative thereof
Related application
The application requires the right of priority of the 61/355th, No. 198 U.S. Provisional Application submitting on June 16th, 2010, and the theme of this U.S. Provisional Application incorporated herein by reference.
Technical field
The application relates to the method that is prepared hydrogenated products and derivative thereof by hexanodioic acid (AA), and this AA obtains from the fermented liquid that contains hexanodioic acid two ammoniums (DAA) or hexanodioic acid one ammonium (MAA).
Background technology
Some carbonaceous product of sugar-fermenting is regarded as the surrogate of petroleum derivation material, with the raw material as manufacturing carbon containing chemical substance.A kind of this class product is AA.Consider so a kind of for from the direct basically method of pure AA and the raw material that this pure AA can be used as the preparation hydrogenated products of preparation of the fermented liquid that contains DAA or the fermented liquid that contains MAA, then provide the mode with economy and environmental protection to prepare such as caprolactone (CLO), 1, the method for the hydrogenated products of 6-hexylene glycol (HDO) and derivative thereof will be useful.
Summary of the invention
The fermented liquid that the invention provides a kind of fermented liquid from the clarification that contains DAA or contain the clarification of MAA prepares the method for hydrogenated products, the method comprises: 100 ℃ to about 300 ℃ temperature and under super-atmospheric pressure, the distillation fermented liquid comprise the top overhead product of water and ammonia with formation and comprise AA and at least about the 20wt%(weight percent) the liquid bottom residue of water; Cooling and/or evaporate described bottoms is to obtain being enough to making described bottoms to be separated into liquid part and as temperature and the composition of the solid-state part of basically pure AA; From described liquid part, isolate described solid-state part; In the presence of at least a hydrogenation catalyst, described solid-state part is carried out hydrogenation comprise at least a hydrogenated products among CLO or the HDO with preparation; With the described hydrogenated products of recovery.
The fermented liquid that the present invention also provides a kind of fermented liquid from the clarification that contains DAA or contained the clarification of MAA prepares the method for hydrogenated products, and the method comprises: ammonia is separated solvent and/or the water azeotropic solvent is added in the fermented liquid; Be enough to form the top overhead product that comprises water and ammonia and comprise AA and at least about the temperature and pressure of the liquid bottom residue of 20wt% water under the described fermented liquid of distillation; Cooling and/or evaporate described bottoms is to obtain being enough to making described bottoms to be separated into liquid part and as temperature and the composition of the solid-state part of basically pure AA; From described liquid part, isolate described solid-state part; In the presence of at least a hydrogenation catalyst, described solid-state part is carried out hydrogenation comprise at least a hydrogenated products among CLO or the HDO with preparation; With the described hydrogenated products of recovery.
Description of drawings
Fig. 1 is the block diagram of biological treatment system;
Fig. 2 illustrates the solubleness of AA in water along with the graphic representation of temperature variation;
Fig. 3 illustrates the hydrogenated products of preparation selection and the schema of derivative thereof.
Embodiment
Should be appreciated that different from appending claims is that hereinafter at least a portion of specification sheets is intended to relate to the representative illustration of the method for selecting for the diagram in the accompanying drawing and is not intended to limit or restriction the present invention.
By being appreciated that method of the present invention with reference to figure 1, Fig. 1 illustrates an exemplary embodiment 10 of method of the present invention with the block diagram form.
Growth container 12 is generally situ steam sterilization fermentation device, can be used for culturing micro-organisms culture (not shown), and this microorganisms cultures is subsequently for the preparation of the fermented liquid that contains DAA, MAA and/or AA.Such growth container is known in the prior art and is not discussed further.
This microorganisms cultures can comprise can be from the microorganism of fermentable carbon source (for example carbohydrate carbohydrate) preparation AA.The representative illustration of microorganism comprises: intestinal bacteria (Escherichia coli or E.coli), aspergillus niger (Aspergillus niger), Corynebacterium glutamicum (Corynebacterium glutamicum) (being also referred to as brevibacterium flavum (Brevibacterium flavum)), enterococcus faecalis (Enterococcus faecalis), veillonella parvula (Veillonella parvula), Actinobacillus succinogenes (Actinobacillus succinogenes), Paecilomyces varioti (Paecilomyces Varioti), yeast saccharomyces cerevisiae (Saccharomyces cerevisiae), Oidium tropicale (Candida tropicalis), bacteroides fragilis (Bacteroides fragilis), bacteroides ruminicola (Bacteroides ruminicola), bacteroides amylophilus (Bacteroides amylophilus), Klebsiella pneumonia (Lebsiella pneumoniae), their mixture etc.
Preferred microorganism comprises: it number is 24887 Oidium tropicale (Candida tropicalis(Castellani) Berkhout that ATCC enters to hide) anamorphic strain OH23; It number is 69875 intestinal bacteria (E.coli) strains A B2834/pKD136/pKD8.243A/pKD8.292 that ATCC enter to hide; Comprise the carrier of expressing cyclohexanone monooxygenase and be named as the intestinal bacteria clay clone body of 5B12,5F5,8F6 and 14D7, this cyclohexanone monooxygenase has by from the SEQ ID NO:1 coding of acinetobacter (Acinetobacter) bacterial strain SE19 and by the aminoacid sequence shown in the SEQ ID NO:2; And the yeast strain (being hereinafter " Verdezyne yeast ") for preparing AA from alkane and other carbon sources that can buy from Verdezyne company limited (Carslbad, CA, the U.S.).
Number be 24887 Oidium tropicale (Candida tropicalis(Castellani) Berkhout by cultivating in 32 ℃ of lower liquid medium withins that ATCC enters to hide) anamorphic strain OH23, can prepare the fermented liquid that contains AA, this liquid nutrient medium is included in the NH of the 300mg in the distilled water of 100ml 4H 2PO 4, 200mg KH 2PO 4, 100mg K 2HPO 4, 50mg MgSO 47H 2The yeast extract of O, 1 μ g vitamin H, 0.1% (w/v, weight/volume) and about 1%(v/v, volume/volume) n-hexadecane.Also can use other substratum, for example contain the YM fermented liquid of n-hexadecane.At document: Okuhura etc., 35Agr.Biol.Chem.1376 also having described by cultivating that ATCC enters to hide (1971) number is 24887 Oidium tropicale (Candida tropicalis(Castellani) Berkhout) anamorphic strain OH23 contains the step of the fermented liquid of AA from the substratum preparation that contains n-hexadecane, and this paper incorporated by reference in the theme of the document.
Also can enter be hidden by ATCC number is the fermented liquid that 69875 coli strain AB2834/pKD136/pKD8.243A/pKD8.292 preparation contains AA.This can be according to hereinafter realizing.Contain IPTG(0.2mM to 1 liter), the overnight culture of the cell of 10 hours coli strain AB2834/pKD136/pKD8.243A/pKD8.292 of growth under 37 ℃ and 250rpm of LB substratum (in the American flask of the Alan of 4L) the inoculation 10ml of Ampicillin Trihydrate (0.05g), paraxin (0.02g) and miramycin (0.05g).But harvested cell is suspended in D-Glucose, shikimic acid (0.04g), the IPTG(0.2mM that 1L contains 56mM again with it), in the M9 minimum medium of Ampicillin Trihydrate (0.05g), paraxin (0.02g) and miramycin (0.05g).Then this culture can be turned back to 37 ℃ of cultivations.After in minimum medium, suspending again, but the pH value of close supervision culture, especially during initial 12 hours.When the pH of culture value reaches 6.5, can add the NaOH of 5N or other an amount of alkali (for example ammonium hydroxide), be back to about 6.8 to adjust the pH value.Accumulation period at 48 hours, the pH value of culture should not be lower than 6.3.In substratum, after 24 hours, in culture supernatants, can detect the suitable of 12mM, the Protocatechuic Acid of suitable-muconate and 1mM and the D-Glucose of 23mM.In substratum after 48 hours, the cell of coli strain AB2834/pKD136/pKD8.243A/pKD8.292 can be basically with 17mM suitable, suitable-muconate replaces the D-Glucose of the 56mM in the substratum.
Then can according to hereinafter go back pathogenic microorganism synthetic suitable, suitable-muconate AA, contain the fermented liquid of AA with preparation.50 milligrams of platinum carbon (10%) can be added to 6ml from fermentation comprise about 17.2mM suitable, suitable-the acellular culture supernatants of muconate in.Then can with the hydrogenation 3 hours at room temperature and under the hydrogen pressure of 50psi of this sample, contain the fermented liquid of AA with preparation.For example, prepared fermented liquid can comprise the approximately AA of 15.1mM by this way.By in containing the substratum of D-Glucose, cultivating, also in Publication about Document, be described with the step that preparation contains the fermented liquid of AA by the cell of cultivating coli strain AB2834/pKD136/pKD8.243A/pKD8.292: Draths﹠amp; Frost, 116J.Am.Chem.Soc.399 (1994); Draths and Frost, 18Biotechnol.Prog.201 (2002); And patent US5,487,987 and patent US 5,616,496, this paper incorporated by reference in the theme of these documents.
Also can by cultivating in as the M9 minimum medium of carbon source and be named as 5B12,5F5,8F6 and 14D7 and comprise the intestinal bacteria clay clone body of expressing by the carrier of the cyclohexanone monooxygenase SEQ ID NO:2 of the SEQ ID NO:1 coding of acinetobacter bacterial strain SE19 being supplemented with 0.4% glucose, prepare the fermented liquid that contains AA.Under 30 ℃, rocked culturing cell 2 hours, and the hexalin of 330ppm is added in the substratum.Subsequently, in other time period for example 2h, 4h or 20h or section At All Other Times, under 30 ℃, further cultivate.Patent US 6,794,165 have also described by cultivating called after 5B12,5F5,8F6 and 14D7 and comprise expression is prepared the fermented liquid that contains AA by the intestinal bacteria clay clone body of the carrier of the cyclohexanone monooxygenase of the SEQ ID NO:1 coding of acinetobacter bacterial strain SE19 step in the substratum that comprises D-Glucose and hexalin, and this paper incorporated by reference in its theme.
Also can utilize (the Carslbad from Verdezyne company limited, CA, the Verdezyne yeast strain preparation that the U.S.) can buy contains the fermented liquid of AA, according on February 8th, 2010, when at the substratum that comprises alkane or other carbon sources (for example sugar and based on the oil of plant) (for example, when cultivating this Verdezyne yeast strain the SD substratum), can prepare AA.
The fermented liquid that the intestinal bacteria that also can be transformed by the nucleic acid of the following material of coding or the preparation of other microorganisms contain AA: succinyl-coenzyme A: acetyl-coenzyme A acyltransferase; 3-hydroxyl acyl-coa dehydrogenase; 3-hydroxyl adipyl-coenzyme A dehydratase; 5-carboxyl-2-amylene acyl-CoA-reductase; Hexanedioyl-coenzyme A synthetic enzyme; Phosphoric acid hexanedioyl transferring enzyme (phosphotransadipylase)/adipic acid ester kinases; Hexanedioyl-thiophorase; Or hexanedioyl-coenzyme A lytic enzyme.Intestinal bacteria or other microorganisms that the fermented liquid that contains AA also can be transformed by the nucleic acid of the following material of coding prepare: succinyl-coenzyme A: acetyl-coenzyme A acyltransferase; 3-oxo hexanedioyl-thiophorase; 3-oxo adipic acid ester reductase enzyme; 3-hydroxyl adipic acid ester dehydratase; With 2-olefin(e) acid ester reductase enzyme.Intestinal bacteria or other microorganisms that the fermented liquid that contains AA also can be transformed by the nucleic acid of the following material of coding prepare: α-ketone hexanedioyl-coenzyme A synthetic enzyme; Phosphoric acid ketone hexanedioyl transferring enzyme (phosphotransketoadipylase)/α-ketoadipic acid ester kinases or α-ketone hexanedioyl-coenzyme A: acetyl-thiophorase; 2-hydroxyl hexanedioyl-coa dehydrogenase; 2-hydroxyl hexanedioyl-coenzyme A dehydratase; 5-carboxyl-2-amylene acyl-CoA-reductase; And hexanedioyl-coenzyme A synthetic enzyme; Phosphoric acid hexanedioyl transferring enzyme/adipic acid ester kinases; Hexanedioyl-coenzyme A: acetyl-thiophorase or hexanedioyl-coenzyme A lytic enzyme.Intestinal bacteria or other microorganisms that the fermented liquid that contains AA also can be transformed by the nucleic acid of the following material of coding prepare: 2-hydroxyl adipic acid ester desaturase; 2-hydroxyl hexanedioyl-coenzyme A synthetic enzyme; Phosphoric acid hydroxyl hexanedioyl transferring enzyme/2-hydroxyl adipic acid ester kinases or 2-hydroxyl hexanedioyl-coenzyme A: acetyl-thiophorase; 2-hydroxyl hexanedioyl-coenzyme A dehydratase; 5-carboxyl-2-amylene acyl-CoA-reductase; And hexanedioyl-coenzyme A synthetic enzyme; Phosphoric acid shifts hexanedioyl enzyme/adipic acid ester kinases; Hexanedioyl-coenzyme A: acetyl-thiophorase; Or hexanedioyl-coenzyme A lytic enzyme.
In standard medium (for example M9 minimum medium), under standard conditions, under the phenotype of keeping conversion necessary suitable antibiotic or nutritional supplement, intestinal bacteria or other microorganisms that can use various carbon source execution to utilize the nucleic acid of encoding such enzymes to transform are fermented.Step, suitable medium and carbon source that the intestinal bacteria that transform by the nucleic acid of cultivating encoding such enzymes or other microorganisms prepare the fermented liquid that contains AA also are described in patent US2009/0305364, and this paper incorporated by reference in its theme.
The step, microorganism strains, suitable medium and the carbon source that prepare the fermented liquid that contains dicarboxylic acid (for example AA) by cultivating yeast saccharomyces cerevisiae (Saccharomyces cerevisiae) bacterial strain or other bacterial strains also are described in patent WO2010/003728, and this paper incorporated by reference in the theme of this patent.
Can be with fermentable carbon source (for example carbohydrate and sugar), nitrogenous source and compound nutrients (for example, corn steep liquor), additional nutrient media components (for example VITAMIN, salt and other can be promoted the material that Growth of Cells and/or product form) and water join in the growth container 12 with the growth that is used for microbiological culture media and keep alternatively.Usually, microbiological culture media is grown under aerobic condition, and this aerobic condition provides by advertising oxygen rich gas (for example, air etc.).Usually, providing acid (for example, sulfuric acid etc.) and ammonium hydroxide to carry out the pH value with the growing period in microorganism culturing controls.
In an example (not shown), by oxygen rich gas being become oxygen-depleted gas (for example, CO 2Deng), and the aerobic condition in the growth container 12 (providing by advertising oxygen rich gas) is converted to anaerobic condition.Anaerobic environment can cause that fermentable carbon source is AA in growth container 12 situ bio-transformations.Provide ammonium hydroxide during AA, to carry out the control of pH value in fermentable carbon source bio-transformation.Owing to there being ammonium hydroxide, prepared AA at least in part (if non-whole) is neutralized to DAA, so that be prepared into the fermented liquid that comprises DAA.Add CO 2Can be provided for preparing the other carbon source of AA.
In another example, the content of growth container 12 can be transferred to independently bio-transformation container 16 by stream 14, so that the carbohydrate source bio-transformation is AA.With oxygen-depleted gas (for example, CO 2Deng) be blasted in the bio-transformation container 16 so that the anaerobic condition that causes preparation AA to be provided.Provide ammonium hydroxide during AA, to carry out the control of pH value in the carbohydrate source bio-transformation.Owing to there being ammonium hydroxide, prepared AA is neutralized to DAA at least in part, so that be prepared into the fermented liquid that comprises DAA.Add CO 2Other carbon source for the preparation of AA is provided.
In another example, bio-transformation can (for example, be carried out under 3-6) in relatively low pH value.Can provide alkali (ammonium hydroxide or ammoniacal liquor) during AA, to carry out the control of pH value in the carbohydrate source bio-transformation.According to required pH value, owing to having ammonium hydroxide or not having ammonium hydroxide, preparation AA, perhaps prepared AA is neutralized at least in part MAA, DAA or comprises the mixture of AA, MAA and/or DAA.Therefore, alternatively, in additional step, by ammoniacal liquor or ammonium hydroxide are provided, AA prepared during the bio-transformation can be neutralized subsequently, produces the fermented liquid that comprises DAA.Therefore, " fermented liquid that contains DAA " typically refers to other components (such as MAA and/or AA) that fermented liquid comprises the DAA that adds by bio-transformation or additive method and/or produce and possible arbitrary quantity.Similarly, " fermented liquid that contains MAA " typically refers to other components (such as DAA and/or AA) that fermented liquid comprises the MAA that adds by bio-transformation or additive method and/or produce and possible arbitrary quantity.
From the bio-transformation of fermentable carbon source (growth container 12 or bio-transformation container 16, the position of depending on the bio-transformation generation) fermented liquid that produces contains insoluble solid usually, such as cellular biomass and other suspended matters, before distillation, described insoluble solid is transferred to clarifying plant 20 by stream 18.Remove insoluble solid and make the fermented liquid clarification.This alleviates or prevents from stopping up subsequently distillation plant.Can remove insoluble solid by any independent technology or the technical combinations in the multiple solid-liquid separation technique, described solid-liquid separation technique includes but not limited to centrifugation and filtration (including but not limited to ultra-filtration, micro-filtration or depth type filtration).Can use the choice of technology as known in the art to filter.Can remove soluble mineral compound by the currently known methods of arbitrary quantity, these currently known methodss are such as but not limited to ion-exchange and physical adsorption etc.
Centrifugation be exemplified as continuous disk centrifugal separator.After centrifugation, it can be useful increasing by essence filtration (polishing filtration) step, this essence is filtered such as for comprising dead-end filtration or the cross flow filter that uses such as the filtration auxiliary means of diatomite etc., perhaps more preferably is ultra-filtration or micro-filtration.Ultrafilter membrane or micro-filtration film for example can be pottery or macromolecular material.An example of polymeric membrane is the ultrafilter membrane of the SelRO MPS-U20P(pH value stabilization of Coriolis filter membrane system company (Koch Membrane Systems) (850 street, Wilmington city, Massachusetts, the U.S.) manufacturing).It is the poly (ether sulfone) film that can buy on market, and molecular weight cut-off is 25,000 dalton, usually at 0.35MPa to the pressure (peak pressure is 1.55MPa) of 1.38MPa and under the temperature up to 50 ° of C, work.Alternatively, can adopt separately the filtration step of ultra-filtration or micro-filtration.
The fermented liquid of the clarification that contains DAA that there is no microorganisms cultures and other solids that produces or the fermented liquid that contains the clarification of MAA are transferred to water distilling apparatus 24 by flowing 22.
The distillation fermented liquid of clarification should contain a certain amount of DAA, this amount account for all dicarboxylic acid di-ammonium salts in the fermented liquid most of at least, preferably at least about 70wt%, 80wt% and most preferably at least about 90wt% more preferably.By high pressure lipuid chromatography (HPLC) (HPLC) or other known methods, can determine that DAA and/or MAA account for the weight percent of the whole dicarboxylates in the fermented liquid (wt%).
Water and ammonia are removed from water distilling apparatus 24 as the top overhead product, and at least a portion water and ammonia are alternatively by stream 26 growth containers 12 that are recycled to bio-transformation container 16(or work under the anaerobism pattern).
As long as distillation is to guarantee that bottoms that the top overhead product that distills contains water and ammonia and distillation comprise at least some AA and carry out at least about the mode of the water of 20wt%, then concrete distillation temperature and pressure are not crucial.The preferred amount of water is at least about 30wt% and further preferred amount is at least about 40wt%.The speed of removing ammonia from distilation steps raises along with temperature and increases, and also can increase this speed by injecting steam (not shown) during distilling.By under vacuum, distilling or advertising described water distilling apparatus by using such as the non-reactive gas of air, nitrogen etc., also can increase the speed of removing ammonia during the distillation.
Removal to water during distilation steps can be strengthened by using organic entrainer, condition is that bottoms contain the water at least about 20wt%, such as toluene, dimethylbenzene, methylcyclohexane, methyl iso-butyl ketone (MIBK), hexanaphthene, heptane etc. of described organic entrainer.If in the presence of the organic reagent that can form azeotropic mixture, distill (this azeotropic mixture is comprised of water and this organic reagent), then distillation produces the two-phase bottoms that comprise water and organic phase, in this case, water can separate with organic phase, and the water bottoms that are used as distilling.As long as the water-content in the bottoms is maintained at the level at least about 30wt%, then basically avoid the by product such as adipimide and adipamide.
The scope that is used for the preferred temperature of distilation steps is approximately 50 ℃ to approximately 300 ℃, and this temperature depends on pressure.Preferred temperature range is approximately 150 ℃ to approximately 240 ℃, and this temperature depends on pressure.Approximately 170 ℃ is preferred to about 230 ℃ distillation temperature." distillation temperature " refers to the temperature (for batch distillation, this temperature can be the temperature when the overhead product of the top of the amount of taking out last expectation) of bottoms.
Adding can separate solvent with the miscible organic solvent of water or ammonia and help to remove ammonia under various distillation temperatures as discussed above and pressure.Such solvent comprises protophobic solvent, dipolar solvent, the oxo solvent of the hydrogen bond that can form inertia.Example includes but not limited to: diglyme, triglyme, tetraethyleneglycol dimethyl ether, sulfoxide (such as methyl-sulphoxide (DMSO)), acid amides (such as dimethyl formamide (DMF) and N,N-DIMETHYLACETAMIDE), sulfone (such as dimethyl sulfone), α-butyrolactone (GBL), tetramethylene sulfone, polyoxyethylene glycol (PEG), butoxytriglycol, N-Methyl pyrrolidone (NMP), ether (such as dioxane) and methyl ethyl ketone (MEK) etc.Such solvent helps to remove ammonia from the DAA of the fermented liquid of clarification or MAA.Which kind of distillation technique no matter, importantly, distillation with guarantee at least some MAA and at least about the water of 20wt% and even the mode more preferably stayed in the bottoms at least about the water of 30wt% carry out.Can be under atmospheric pressure, under the sub-atmospheric pressure or distill under the super-atmospheric pressure.
Under other conditions, such as when not existing entrainer or ammonia to separate to distill under the solvent, under super-atmospheric pressure and distilling to form the top overhead product that comprises water and ammonia to about 300 ℃ the temperature and comprising AA and at least about the liquid bottom residue of the water of 20wt% greater than 100 ℃.Super-atmospheric pressure usually drops on greater than ambient atmosphere and is pressed onto approximately in the scope in 25 normal atmosphere.Advantageously, the amount of water is at least about 30wt%.
This distillation can be single stage flash, multistage distillation (that is, Multistage tower-type distillation) etc.Single stage flash can be carried out in the flasher (for example, luwa evaporator, thin-film evaporator, thermosiphon flasher and pump circulation flasher etc.) of arbitrary type.The multistage distillation tower can be by realizing with column plate and filler etc.Described filler can be random fill (for example, Raschig ring, Pall ring and Berl saddle packing etc.) or structured packing (for example, Koch-Sulzer filler, Ying Teluokesi (Intalox) filler and Mai Lepaike (Mellapak) etc.).Described column plate can be arbitrary design (for example, sieve tray, valve tray, bubble cap plate etc.).Can under the theoretical stage of arbitrary quantity, carry out described distillation.
If described water distilling apparatus is tower, then structure is not special key, and can design this tower with the rule of knowing.Can under air lift pattern, rectifying pattern or fractionation pattern, operate this tower.Can distill with batch mode, semi continuous or continuous mode.In continuous mode, fermented liquid is sent into described water distilling apparatus continuously, and top overhead product and bottoms are removed continuously from described device along with their formation.From the distillation overhead product be ammonia/aqueous solution, and the distillation bottoms be the liquid solution of MAA and AA, the bottoms of described distillation also can contain other fermentation byproduct salts (that is, ammonium acetate, ammonium formiate, DL-Lactic acid ammonium salt etc.) and chromoplastid.
The bottoms of described distillation can be transferred to refrigerating unit 30 and pass through conventional method cooling by flowing 28.Cooling technology is not critical.Can use heat exchanger (utilizing recovery of heat).Can use flash cooler that described bottoms cooling is low to moderate approximately 15 ℃.Usually utilize refrigeration coolant cools to 15 ℃, such as, ethylene glycol solution, perhaps, salt solution more preferably.Can comprise that before cooling enrichment step is to help to increase product output.In addition, can adopt currently known methods will concentrate and cool off combination, such as the heat extraction method of vacuum-evaporation and employing use integral type cooling jacket and/or external heat exchanger.
Research is found, the having of some MAA in the liquid bottom residue helps to cause with the type of cooling by the solubleness that reduction contains the AA in the liquid aqueous bottoms of MAA bottoms are separated into the liquid part that contact with solid-state part, and described solid-state part at least " substantially by " AA forms (meaning is that described solid-state part is at least basically pure crystalline A A).Fig. 2 illustrates the solubleness of AA in water.Therefore, research finds, if some MAA also are present in the aqueous solution, then AA can be more completely crystallization and going out from this aqueous solution.The preferred concentration of MAA is about 20wt% in such solution.The more preferably concentration of MAA in such solution be ppm(1,000,000/) to the about scope of 3wt%.This phenomenon is so that AA crystallization under the high temperature of temperature required when not having MAA (, the formation of the solid-state part of the bottoms of distillation).
The bottoms of distillation are sent in the separator 34 to isolate solid-state part from liquid part by flowing 32.Can realize separating by press filtration (for example, using Nutsche type pressure filter or Rosenmond type pressure filter), centrifugal etc.The solid product that produces can be reclaimed as product 36, and if necessary, carry out drying by standard method.
At after separating, may expect to process solid-state part to guarantee not having liquid part to remain on the surface of solid-state part.Make the minimized a kind of mode of amount of the lip-deep liquid part that remains in this solid-state part be, the dry (not shown) of the solid-state part of washing that washes the solid-state part of separating with water and will obtain.To use so-called " centrifugal basket drier " (not shown) in order to the easily mode of washing described solid-state part.From TheWestern States Machine Company(Hamilton, Ohio, the U.S.)) can buy suitable centrifugal basket drier.
The liquid part (that is, mother liquor) of the bottoms 34 of distillation can contain the AA of remaining dissolving, any unconverted MAA, any fermentation byproduct (such as ammonium acetate, DL-Lactic acid ammonium salt or ammonium formiate) and other a small amount of impurity.This liquid part can be sent to downstream unit 40 by stream 38.In an example, this downstream unit 40 can be for being used to form the device of deicing agent, for example, and by with an amount of potassium hydroxide treatment mixture, so that ammonium salt is changed into sylvite.The ammonia that produces in this reaction can be recovered, with at bio-transformation container 16(or the growth container 12 of working under the anaerobism pattern) in recycle.The Kalisalt mixture that obtains is valuable as deicing agent and deicing agent.
Mother liquor from solid separating step 34 can strengthen the recovery of AA and further MAA is converted into AA with further by stream 42 recirculation (or part recirculation) to water distilling apparatus 24.
The solid-state part of the crystallization that causes take the type of cooling is as basically pure AA and therefore can be used for the known application of AA.
HPLC can be used for detecting the existence of nitrogenous impurity (such as adipamide and adipimide).Can measure by elemental carbon and nitrogen analysis the purity of AA.Ammonia electrode can be used for measuring the rough approximation value of AA purity.
Drop into according to environment and various operation, exist fermented liquid or to contain the situation of fermented liquid of the clarification of AA for the fermented liquid of the clarification that contains MAA.In these cases, can be advantageously, MAA, DAA and/or AA and optional ammoniacal liquor and/or ammonium hydroxide are joined in these fermented liquids so that the substantially pure AA of preparation.For example, can set the working pH value of fermented liquid so that this fermented liquid is the fermented liquid that contains the fermented liquid of MAA or contain AA.MAA, DAA, AA, ammoniacal liquor and/or ammonium hydroxide can be joined in these fermented liquids to obtain preferably less than 6 fermented liquid pH value so that prepare above-mentioned basically pure AA.In a concrete form, particularly advantageously be to make AA, MAA and the water recycle of the liquid bottom residue that produces since distilation steps 24 to enter the fermented liquid of described fermented liquid and/or clarification.About containing the fermented liquid of MAA, such fermented liquid typically refers to, and this fermented liquid comprises other compositions (such as DAA and/or AA) of the MAA that adds by bio-transformation or additive method and/or produce and possible arbitrary quantity.
As shown in Figure 3, under selected temperature and pressure, comprise that the stream of AA can contact to prepare the hydrogenated products that comprises CLO and/or HDO with hydrogen with hydrogenation catalyst.The temperature that raises and the pressure of rising are preferred.
The main component that is used for the catalyzer of SA hydrogenation can be selected from the metal of palladium, ruthenium, rhenium, rhodium, iridium, platinum, nickel, cobalt, copper, iron, its mixture and combination thereof.
Chemical promoter can improve the activity of catalyzer.Can during any stage in the chemical treatment of catalyst component promotor be incorporated in the catalyzer.Chemical promoter strengthens physical function or the chemical functional of catalyzer usually, but also can add chemical promoter stops the side reaction of not expecting.Be selected from the metal of tin, zinc, copper, gold and silver and combination thereof suitable promotor comprising.Preferred metallic promoter agent is tin.Spendable other promotor being is selected from the element of I family and the II family of the periodic table of elements.
Catalyzer can have carrier or carrier free.Loaded catalyst is a kind of like this catalyzer, wherein active catalyzer is deposited on the solid support material by many methods, for example spray, embathe or physical mixed, subsequent drying, calcining and if necessary the method by for example reduction or oxidation activate.Material through being commonly used for carrier can be for having the porosu solid of large total surface area (outside and inner), and this porosu solid can provide the catalyzer of per unit weight that the avtive spot of high density is arranged.Support of the catalyst can strengthen the function of catalyzer.Load type metal catalyst is that catalyzer is the loaded catalyst of metal.
The catalyzer that is not carried on the catalyst support material is unsupported catalyst.For example, unsupported catalyst can be platinum black or
Figure BDA00002583409900121
(W.R.Grace﹠amp; Co., Colombia, MD) catalyzer.Because optionally leaching contains the alloy of reactive metal and leachable metal (being generally aluminium), therefore
Figure BDA00002583409900122
Catalyzer has high surface-area.
Figure BDA00002583409900123
Lower temperature is used in the active and permission that catalyzer is high because higher specific surface area has in hydrogenation.
Figure BDA00002583409900124
The reactive metal of catalyzer comprises nickel, copper, cobalt, iron, rhodium, ruthenium, rhenium, osmium, iridium, platinum, palladium, its mixture and combination thereof.
Also promoter metals can be added to the basis In the metal with the impact
Figure BDA00002583409900126
Selectivity of catalyst and/or activity.Be used for
Figure BDA00002583409900127
The optional transition metal that arrives VIIIA family, IB family and IIB family since the IIIA of periodic table of elements family of the promoter metals of catalyzer.The example of promoter metals comprises chromium, molybdenum, platinum, rhodium, ruthenium, osmium and palladium, usually accounts for approximately 2% of metal gross weight.
Support of the catalyst can be any solid-state inert substance, includes but not limited to: oxide compound, for example silicon-dioxide, aluminum oxide and titanium dioxide; Barium sulfate; Calcium carbonate and carbon.Support of the catalyst can be the form of powder, particle, ball shape etc.
Preferred carrier substance can be selected from carbon, aluminum oxide, silicon-dioxide, silica-alumina, silica-titania, titanium dioxide, titanium dioxide-aluminum oxide, barium sulfate, calcium carbonate, Strontium carbonate powder, its mixture and combination thereof.Load type metal catalyst also can have the carrier substance of being made by one or more compounds.Preferred carrier is carbon, titanium dioxide and aluminum oxide.Preferred carrier is surface-area greater than about 100m 2The carbon of/g.Further preferred carrier is surface-area greater than about 200m 2The carbon of/g.Preferably, by the support of the catalyst weighing scale, carbon has less than about 5% ash content.Ash content is residual inorganic residues (being expressed as the percentage ratio of the original weight of carbon) after carbon burns.
Add vehicle weight based on metal catalyst weight, the preferred content of metal catalyst can be approximately 0.1% to approximately 20% of this loaded catalyst in the loaded catalyst.Preferred metal catalyst content scope is approximately 1% to approximately 10% of loaded catalyst.
The combination of metal catalyst and carrier system can comprise any metal of mentioning and any carrier of mentioning herein herein.The preferably combination of metal catalyst and carrier comprises the palladium that is carried on the carbon, be carried on the palladium on the aluminum oxide, be carried on the palladium on the titanium dioxide, be carried on the platinum on the carbon, be carried on the platinum on the aluminum oxide, be carried on the platinum on the silicon-dioxide, be carried on the iridium on the silicon-dioxide, be carried on the iridium on the carbon, be carried on the iridium on the aluminum oxide, be carried on the rhodium on the carbon, be carried on the rhodium on the silicon-dioxide, be carried on the rhodium on the aluminum oxide, be carried on the nickel on the carbon, be carried on the nickel on the aluminum oxide, be carried on the nickel on the silicon-dioxide, be carried on the rhenium on the carbon, be carried on the rhenium on the silicon-dioxide, be carried on the rhenium on the aluminum oxide, be carried on the ruthenium on the carbon, be carried on ruthenium and the ruthenium that is carried on the silicon-dioxide on the aluminum oxide.
The further preferred combination of metal catalyst and carrier comprises the ruthenium that is carried on the carbon, be carried on ruthenium on the aluminum oxide, be carried on palladium on the carbon, be carried on palladium on the aluminum oxide, be carried on palladium on the titanium dioxide, be carried on platinum on the carbon, be carried on platinum on the aluminum oxide, be carried on the rhodium on the carbon and be carried on rhodium on the aluminum oxide.
Preferred carrier is carbon.Further preferred carrier is the BET surface-area less than about 2000m 2The carrier of/g, especially carbon.Further preferred carrier is that surface-area is about 300m 2/ g to 1000m 2The carrier of/g, especially carbon.
Usually, about 100 ℃ to about 300 ℃ temperature, maintaining about 6MPa to the reactor of about 20MPa pressure, carry out hydrogenation.
Utilize catalyzer to make to contain the method for the charging hydrogenation of AA to be undertaken by various operator schemes well known in the prior art.Therefore, can utilize fixed-bed reactor, various types of slurry attitude stirred reactor (no matter being gas stirring type or mechanical stirring) etc. to carry out whole hydrogenation process.Can under batch mode or continuous mode, carry out hydrogenation process, wherein, contain the water of hydrogenation precursor and contact with under high pressure the gas phase that contains hydrogen and granular solid catalyst.
Temperature, solvent, catalyzer, reactor configurations, pressure and mixture ratio are for affecting the parameter of hydrogenation.Relation between these parameters of capable of regulating is with desired conversion, speed of reaction and selectivity in the reaction that realizes the method.
Preferred temperature is approximately 25 ℃ to 350 ℃, more preferably from approximately 100 ℃ to approximately 350 ℃, most preferably from approximately 150 ℃ to 300 ℃.Hydrogen pressure is preferably about 0.1MPa to about 30MPa, more preferably is about 1MPa to 25MPa, and is most preferably approximately 1MPa to 20MPa.
Can under the condition of not adding solvent, can in water or in the presence of organic solvent, carry out this reaction.Water is preferred solvent.Useful organic solvent comprises solvent known in the field of hydrogenation, for example hydrocarbon polymer, ether and alcohol.Most preferably being alcohol, especially is lower alcohol, for example methyl alcohol, ethanol, propyl alcohol, butanols and amylalcohol.Should be to carry out this reaction at least about the selectivity in 70% the scope.At least 85% selectivity is typical.Selectivity is that the material that transforms is the weight percent of CLO and HDO, and wherein, the material that transforms is the part of the participation hydrogenation of initial substance.
Can or in being generally used for arbitrary equipment of successive processes, carry out the method with continuous mode with batch mode, order batch mode (being a series of batch reactor).The separation method that separates by being generally used for this class removes the water of condensation that forms as reaction product.
Preferred hydrogenation reactor can be under hydrogen pressure and is operated in the presence of the catalyzer of the ordered structure that is selected from Ru, Re, Sn, Pb, Ag, Ni, Co, Zn, Cu, Cr, Mn or its mixture of catalytic amount.Can control hydrogen pressure and the hydrogenated products of temperature to obtain expecting of reactor.Usually, the reactor feed that is used for hydrogenation maintains approximately 100 ℃ to approximately 210 ℃, but more preferably maintains approximately 135 ℃ to approximately 150 ℃.
The selection of hereinafter having described from AA transforms.For example, patent US 6,495, and 730 disclose the hydrogenation of AA to HDO.Embodiment 10 discloses following methods: in the reactor of the 30ml that the Ru-Sn-Re catalyzer of the AA of the ion exchanged water of 5g, 2.10g and 0.30g can be packed into.Can at room temperature with the air in the nitrogen replacement reactor, then the hydrogen under the 2.0MPa be imported in this reactor, and can make the internal temperature of reactor rise to 240 ℃.When this internal temperature rises to after 240 ℃, can import the hydrogen of pressurization so that internal pressure increases to 9.8MPa.Then, under the temperature that can mention and under the hydrogen pressure of mentioning, carried out hydrogenation 3.5 hours in the above in the above.After finishing hydrogenation, can content be separated into supernatant liquor and catalyzer by decant.Can use the catalyzer 5 times that 1ml ion-exchange water washing reclaims, and the water that is used for washing can mix with supernatant liquor mentioned above, resulting mixture is as reaction mixture.Under condition mentioned above, the reaction mixture that can utilize HPLC and gas chromatography (GC) analyses to obtain is with the conversion of definite initial substance and the productive rate of primary alconol.The analysis showed that among the embodiment 10, the transformation efficiency of AA be 100% and the productive rate of HDO be 96%.
Patent US5,969,194 disclose: a) in the presence of the Ru-Sn-Pt/ activated carbon catalyst and under 10MPa pressure and 240 ℃, make AA be hydrogenated to HDO(81.4% by 6 hours hydrogenizations, productive rate); And b) under identical reaction conditions, make CLO be hydrogenated to HDO, productive rate is 72.4%.
Patent US 5,981, and 769 disclose by AA and prepare simultaneously HDO and CLO.Can separate HDO and CLO by distillating method known in the art.In addition, can make CLO partly or wholly be recycled to step of hydrogenation so that the productive rate maximization of HDO.
Behind the preparation CLO, can prepare hexanolactam (CL), for example by patent US 3,401,161 disclosed method preparations.In the method, under 330 ℃ the temperature and under the pressure at 9.12MPa to 12.67MPa, heating CLO, ammonia and dioxane 7 hours.Then, reaction mixture, and carry out underpressure distillation at first to remove dioxane, then remove CL.The productive rate of CL is 60%.
Behind the preparation CLO, can prepare HDO, for example by patent US 4,652,685 disclosed method preparations, the method is used the chromous acid ketone catalyst of fixed-bed reactor and reduction.Approximately reacting under 160 ℃ to 230 ℃ the temperature.Similarly, in patent JP 11/255684 (A), by using Ru-Sn loaded catalyst, an alkali metal salt and alkaline earth salt, in liquid phase reaction, CLO is carried out hydrogenation and obtains HDO.Patent JP 2000/159705 (A) has also described by CLO and has prepared HDO.Therefore, in the presence of catalyzer, 6-caprolactone is carried out hydrogenation to obtain the 98.1mol%(molar percentage) 1, the 6-hexylene glycol, by the heating CuSO 45H 2O, FeSO 47H 2O, Al 2(SO 4) 318H 2O and Na 2CO 3And under 750 ℃, its calcining is prepared this catalyzer.
Another purposes of CLO is gathered-CLO for preparation, as disclosed among the patent JP 11/349670 (A).
Patent US 6,495,730, patent US 5,969, and 164, patent US 5,981,769, patent US4,652,685, patent US 3,401,161, this paper incorporated by reference in the theme of patent JP11/255684 (A), patent JP 2000/159705 (A) and patent JP 11/349670 (A).
Embodiment
By following nonrestrictive exemplary embodiment method of the present invention is described.
Because of the solubleness of the typical fermentation byproduct in the real attenuation liquid in the method for the present invention, the use of synthetic DAA solution is considered to the good model for the characteristic of this real attenuation liquid.The Main By product that produces between yeast phase is ammonium acetate, DL-Lactic acid ammonium salt and ammonium formiate.Ammonium acetate, DL-Lactic acid ammonium salt and the ammonium formiate solubleness in water is obviously large than AA, and these three kinds of materials all usually are present in the fermented liquid with 10% concentration less than DAA concentration.In addition, even when forming acid (acetic acid, formic acid and lactic acid) during distilation steps, these acid are miscible and will not crystallization from water with water.This means that AA reaches capacity and crystallization from solution (that is, forming solid-state part), stay sour impurity and be dissolved in the mother liquor (that is, liquid part).
Embodiment 1
This embodiment shows DAA to the conversion of MAA.
Make the round-bottomed flask of 1L that synthetic 4.5% the DAA solution of 800g is housed.This flask is equipped with five column plate Oldershaw sections (a five tray Oldershaw section), and the top of this Oldershaw section has still head.Overhead product is collected in the ice-cold receptor.Utilize the content of heating jacket heating flask, and utilize magnetic stirrer.Begin to distill and collect the overhead product of 719.7 grams.Measure overhead product with volumetry, show that it is 0.29% ammonia solution (that is, approximately 61% DAA changes into MAA).From flask, remove heat residue (76g) and place it in the erlenmeyer flask, place a weekend, during slowly cool to while stirring room temperature.Then, be accompanied by stirring, content is cooled to 15 ℃ and kept 60 minutes, then be cooled to 10 ℃ and kept 60 minutes, be cooled at last 5 ℃ and kept 60 minutes.Cross filter solid and under 75 ℃ in vacuum oven dry 2 hours, obtain 16.2 gram solids.To the analysis showed that the ammonia content of solid carries out, the molar ratio of ammonia and AA is approximately 1:1 by ammonia electrode.
Embodiment 2
This embodiment shows MAA to the conversion of AA.
Make the Parr autoclave of 300ml that 80g synthetic MAA and 124g water are housed.Sealing autoclave, and stir content and be heated to approximately 200 ℃ (autogenous pressures be approximately 203psig).In case content reaches this temperature, water is sent into autoclave and utilize back pressure regulator with approximately 2g/ minute speed steam to be shifted out from autoclave with approximately 2g/ minute speed.Make the vapor condensation that leaves autoclave and be collected in the receptor.Autoclave operates under these conditions, until send into the water that amounts to 1210g and amount to the overhead product of collecting 1185g.Content (209g) part of autoclave is cooled off, and it is removed from reactor.With slurries in the American flask of Alan, at room temperature stir and spend the night.Then wash solid with dope filtration, and with 25g water.In vacuum oven, descend dry moist solids 1 hour at 75 ℃, obtain 59g AA product.The ammonium ion that contains 0.015mmol by the every gram solid of the analysis showed that of ammonium ion electrode.The fusing point of the solid that reclaims is 151 ℃ to 154 ℃.
Embodiment 3
This embodiment shows the conversion of DAA to MAA in the presence of solvent.
With the concentrated ammonium hydroxide of the distilled water of 36.8g and the 19.7g beaker of packing into.Then, the hexanodioic acid that slowly adds 23.5g.Then the formation clear liquid that stirs the mixture is placed on this clear liquid in the round-bottomed flask of the 500mL that contains stirring rod.Then triglyme (80g) is joined in this flask.Then five column plates 1 are equipped with, this flask " the Oldershaw section, the top of this Oldershaw section has still head.Still head is furnished with ice bath cooled receptor.This distilling flask also is equipped with the feed hopper that contains 150g distilled water.Then stir content, and utilize heating jacket heating content.When overhead product begins to occur, the water in the feed hopper is dropwise joined in the flask to remove identical speed with overhead product.When all water of adding in the feed hopper, distillation stops.Collected the overhead product that amounts to 158g.Volumetry is measured overhead product and is shown 1.6% ammonia content.46% of the ammonia that this is equivalent to pack into.In other words, residue is that ratio is the mixture of 91/9 hexanodioic acid one ammonium/hexanodioic acid two ammoniums.After residue is cooled to room temperature, place it in the erlenmeyer flask of 250mL, slowly cool to while stirring 5 ℃.Filter slurries, then dry wet crystal 2 hour in vacuum oven obtains the 5.5g solid.Solid analysis shows, the ratio of ammonium ion and hexanodioic acid radical ion is essentially 1:1(namely, hexanodioic acid one ammonium).
Embodiment 4
This embodiment shows in the presence of solvent MAA to the conversion of AA.
Make beaker that the distilled water of 46.7g and the concentrated ammonium hydroxide of 9.9g are housed.Then, the hexanodioic acid that slowly adds 23.5g.Then the formation clear liquid that stirs the mixture is placed on this clear liquid in the 500mL round-bottomed flask that contains stirring rod.Then triglyme (80g) is added in this flask.Then five column plates 1 are equipped with, this flask " the Oldershaw section, the top of this Oldershaw section has still head.Still head is furnished with ice bath cooled receptor.This matrass also is furnished with the feed hopper that contains 1800g distilled water.Then stir content, and utilize heating jacket heating content.When overhead product begins to occur, the water in the feed hopper is dropwise joined in the flask to remove identical speed with overhead product.When adding water all in the feed hopper, distillation stops.Arrived and collected the overhead product that amounts to 1806.2g.Volumetry is measured overhead product and is shown 0.11% ammonia content.72% of the ammonia that this is equivalent to pack into.In other words, residue is that ratio is the mixture of hexanodioic acid/hexanodioic acid one ammonium of 72/28.Residue is placed in the erlenmeyer flask, stirs and be cooled to 0 ℃, and left standstill 1 hour.Filter slurries, obtain the wet cake of 18.8g and the mother liquor of 114.3g.Then, 80 ℃ of lower vacuum-drying solids 2 hours, obtain the 13.5g solid.Then with this dissolution of solid in 114g hot water, then be cooled to 5 ℃, continue to stir 45 minutes.Filter slurries, obtain the wet solid of 13.5g and the mother liquor of 109.2g.80 ℃ of lower vacuum-drying solids 2 hours, obtain the drying solid of 11.7g.Solid analysis shows, the content of ammonium ion be 0.0117mmol/g(namely, pure hexanodioic acid basically).
Although in conjunction with concrete steps and its formal description method of the present invention, yet, should be appreciated that a large amount of equivalents can substitute element and the step of appointment described herein, and do not break away from the spirit and scope of the present invention of describing in the appended claims.
Figure IDA00002739300500021
Figure IDA00002739300500031
Figure IDA00002739300500041

Claims (8)

1. method that is used for preparing from the fermented liquid of the clarification that contains hexanodioic acid two ammonium DAA or the fermented liquid that contains the clarification of hexanodioic acid one ammonium MAA hydrogenated products, described method comprises:
(a) exist〉100 ℃ to approximately 300 ℃ temperature and under super-atmospheric pressure, distill described fermented liquid and comprise the top overhead product of water and ammonia with formation and comprise hexanodioic acid AA and weight percent is at least about the liquid bottom residue of 20% water;
(b) cool off and/or evaporate described bottoms, to obtain being enough to making described bottoms to be separated into liquid part and as temperature and the composition of the solid-state part of basically pure AA;
(c) from described liquid part, isolate described solid-state part;
(d) in the presence of at least a hydrogenation catalyst, described solid-state part is carried out hydrogenation comprise at least a hydrogenated products among caprolactone CLO or 1, the 6-hexylene glycol HDO with preparation; With
(e) reclaim described hydrogenated products.
2. method that is used for preparing from the fermented liquid of the clarification that contains DAA or the fermented liquid that contains the clarification of MAA hydrogenated products, described method comprises:
(a) ammonia being separated solvent and/or water azeotropic solvent is added in the described fermented liquid;
(b) being enough to form the top overhead product that comprises water and ammonia and comprising AA and weight percent is at least about under the temperature and pressure of liquid bottom residue of 20% water, distill described fermented liquid;
(c) cool off and/or evaporate described bottoms, to obtain being enough to making described bottoms to be separated into liquid part and as temperature and the composition of the solid-state part of basically pure AA;
(d) from described liquid part, isolate described solid-state part;
(e) in the presence of at least a hydrogenation catalyst, described solid-state part is carried out hydrogenation comprise at least a hydrogenated products among CLO or the HDO with preparation; With
(f) reclaim described hydrogenated products.
3. each described method in 2 according to claim 1 also is included under the pressure of the temperature of rising and rising and makes CLO contact to prepare hexanolactam CL with the ammonia source.
4. method according to claim 3 also comprises making described CL change into nylon 6.
5. each described method in 2 according to claim 1 also comprises described CLO is changed into poly--CLO.
6. each described method in 2 according to claim 1 also comprises:
Make described CLO contact to prepare the hydrogenated products that comprises HDO with hydrogen with at least a hydrogenation catalyst; And
Reclaim described HDO.
7. each described method in 2 according to claim 1, wherein, described fermented liquid is by obtaining carbon source through fermentation in the presence of microorganism, and described microorganism is selected from: it number is 24887 Oidium tropicale (Castellani) anamorphic strain OH23 that ATCC enter to hide; It number is 69875 coli strain AB2834/pKD136/pKD8.243A/pKD8.292 that ATCC enter to hide; The intestinal bacteria clay clone body 5B12 that comprises the carrier of expressing the cyclohexanone monooxygenase of being encoded by SEQ ID NO:1; The intestinal bacteria clay clone body 5F5 that comprises the carrier of expressing the cyclohexanone monooxygenase of being encoded by SEQ IDNO:1; The intestinal bacteria clay clone body 8F6 that comprises the carrier of expressing the cyclohexanone monooxygenase of being encoded by SEQ ID NO:1; The intestinal bacteria clay clone body 14D7 that comprises the carrier of expressing the cyclohexanone monooxygenase of being encoded by SEQ ID NO:1; With the Verdezyne yeast.
8. method according to claim 2, wherein, separate in the presence of the solvent or the described fermented liquid of distillation in the presence of the water azeotropic solvent at ammonia, it is be selected from diglyme, triglyme, tetraethyleneglycol dimethyl ether, sulfoxide, acid amides, sulfone, polyoxyethylene glycol PEG, butoxytriglycol, N-Methyl pyrrolidone NMP, ether and methyl ethyl ketone MEK at least a that described ammonia separates solvent, and described water azeotropic solvent is be selected from toluene, dimethylbenzene, methylcyclohexane, methyl iso-butyl ketone (MIBK), hexane, hexanaphthene and heptane at least a.
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